CN102557939B - Method for preparing ethyl acetoacetate - Google Patents
Method for preparing ethyl acetoacetate Download PDFInfo
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- CN102557939B CN102557939B CN2011104526614A CN201110452661A CN102557939B CN 102557939 B CN102557939 B CN 102557939B CN 2011104526614 A CN2011104526614 A CN 2011104526614A CN 201110452661 A CN201110452661 A CN 201110452661A CN 102557939 B CN102557939 B CN 102557939B
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- aceto acetate
- methyl aceto
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Abstract
The invention relates to a method for preparing ethyl acetoacetate. The method comprises the following steps of: allowing gasified ethanol to continuously pass through a fixed bed reactor with a catalyst layer, and reacting to obtain the ethyl acetoacetate, wherein the reaction temperature is 200 to 700 DEG C; and the catalyst layer comprises the following components in percentage by weight: 10 to 25 percent of copper, 15 to 35 percent of zinc, 5 to 15 percent of aluminum, 4 to 20 percent of nickel, 2 to 8 percent of alumina, 1 to 6 percent of copper oxide, 3 to 9 percent of zinc oxide and 4 to 10 percent of nickel oxide. The method is continuously operated; raw materials are cheap; three wastes are basically avoided; and the process is simple, low in cost and high in safety.
Description
Technical field
The present invention relates to a kind of preparation method of methyl aceto acetate.
Background technology
Methyl aceto acetate is a kind of very important organic synthesis intermediate, can be used to preparation medicine, agricultural chemicals, dye well spices etc.At present, the industrialized preparing process of conventional methyl aceto acetate mainly contains two kinds: the one,, utilize acetic acid under triethyl phosphate exists, first cracking generates ketene, dimerization generates ketene dimer again, carry out esterification by ketene dimer and dehydrated alcohol under sulphuric acid catalysis and generate methyl aceto acetate, the gained crude product obtains finished product through underpressure distillation; The 2nd,,, take ethyl acetate as raw material, with sodium Metal 99.5 or sodium ethylate, prepare methyl aceto acetate.In these two kinds of methods, the former exists equipment corrosion serious, and ketene dimer toxicity is large, environmental hazard is seriously waited deficiency, and latter's cost is too high, and the three wastes are many especially and danger is very large.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of novel method for preparing methyl aceto acetate is provided.
For solving above technical problem, the present invention takes following technical scheme:
A kind of preparation method of methyl aceto acetate, it is that the ethanol after gasification is reacted and generates methyl aceto acetate by the fixed-bed reactor that are provided with catalyst layer continuously, temperature of reaction is 200 ℃～700 ℃, in weight percentage, described catalyst layer is comprised of following component: copper 10%～25%, zinc 15%～35%, aluminium 5%～15%, nickel 4%～20%, aluminum oxide 2%～8%, cupric oxide 1%～6%, zinc oxide 3%～9%, nickel oxide 4%～10%.
The temperature of described reaction is preferably 300 ℃～500 ℃, more preferably 350 ℃～450 ℃.
The volume space velocity of ethanol is preferably 2000～8000h
-1, 4000～6000h more preferably
-1
The mol ratio of ethanol and catalyzer is preferably 0.3～4: 1, more preferably 1.5～2.5: 1.
Preferably, in the ethanol after gasification, the content of ethanol is more than 99wt%.
According to further embodiment of the present invention: after reaction finished, the product solution that contains methyl aceto acetate was collected in condensation, and rectification under vacuum, obtain purity at the methyl aceto acetate finished product more than 99%.Preferably, reclaim unreacted ethanol and re-using in reaction.
Due to the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention is take the ethanol of cheapness as raw material, the heating and gasifying relief its by being fixed with the reaction bed of special catalyst, under hot conditions and catalyst action, occur between ethanol molecule to reset and dehydrogenation reaction, generate methyl aceto acetate,, by the rectification under vacuum of routine, can obtain purity greater than the methyl aceto acetate finished product more than 99%.The inventive method operate continuously, cost of material is cheap again, there is no the three wastes, and technique is simple, and cost is low, security good.
Embodiment
The present invention is take ethanol as raw material, and the reaction formula that generates methyl aceto acetate is as follows:
The present invention will be further described in detail below in conjunction with specific embodiment.
Embodiment 1
Add the catalyzer of the metal oxides such as the metals such as copper, zinc, aluminium, nickel and aluminum oxide, cupric oxide, zinc oxide, nickel oxide in diameter 25mm, length 1000mm fixed-bed reactor, by copper 20%, zinc 28%, aluminium 11%, nickel 16% and aluminum oxide 6%, cupric oxide 4%, zinc oxide 8%, nickel oxide 7% weight, formed.The outer electric-heating-wire-heating of using, control temperature by voltate regulator, passes into ethanol, and 420 ℃ of temperature of reaction, reactant air speed are 5500h
-1, the mol ratio of ethanol and catalyzer is 1.9: 1, the primary first-order equation molar yield of methyl aceto acetate reaches 63%.
Embodiment 2
Add the catalyzer of the metal oxides such as the metals such as copper, zinc, aluminium, nickel and aluminum oxide, cupric oxide, zinc oxide, nickel oxide in diameter 20mm, length 800mm fixed-bed reactor, by copper 23%, zinc 31%, aluminium 13%, nickel 18% and aluminum oxide 3%, cupric oxide 3%, zinc oxide 4%, nickel oxide 5% weight, formed.The outer electric-heating-wire-heating of using, control temperature by voltate regulator, passes into ethanol, and 390 ℃ of temperature of reaction, reactant air speed are 6500h
-1, the mol ratio of ethanol and catalyzer is 2.7: 1, the primary first-order equation molar yield of methyl aceto acetate reaches 52%.
Embodiment 3
Add the catalyzer of the metal oxides such as the metals such as copper, zinc, aluminium, nickel and aluminum oxide, cupric oxide, zinc oxide, nickel oxide in diameter 25mm, length 1200mm fixed-bed reactor, by copper 17%, zinc 27%, aluminium 10%, nickel 15% and aluminum oxide 7%, cupric oxide 6%, zinc oxide 9%, nickel oxide 9% weight, formed.The outer electric-heating-wire-heating of using, control temperature by voltate regulator, passes into ethanol, and 450 ℃ of temperature of reaction, reactant air speed are 4500h
-1, the mol ratio of ethanol and catalyzer is 2.2: 1, the primary first-order equation molar yield of methyl aceto acetate reaches 56%.
Above-described embodiment only is explanation technical conceive of the present invention and characteristics; its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. the preparation method of a methyl aceto acetate, it is characterized in that: the method is that the ethanol after gasification is reacted and generates methyl aceto acetate by the fixed-bed reactor that are provided with catalyst layer continuously, temperature of reaction is 200 ℃～700 ℃, in weight percentage, described catalyst layer is comprised of following component: copper 10%～25%, zinc 15%～35%, aluminium 5%～15%, nickel 4%～20%, aluminum oxide 2%～8%, cupric oxide 1%～6%, zinc oxide 3%～9%, nickel oxide 4%～10%.
2. the preparation method of methyl aceto acetate according to claim 1, it is characterized in that: the temperature of described reaction is 300 ℃～500 ℃.
3. the preparation method of methyl aceto acetate according to claim 2, it is characterized in that: the temperature of described reaction is 350 ℃～450 ℃.
4. the preparation method of methyl aceto acetate according to claim 1, it is characterized in that: the volume space velocity of ethanol is 2000～8000h
-1
5. the preparation method of methyl aceto acetate according to claim 4, it is characterized in that: the volume space velocity of ethanol is 4000～6000h
-1
6. the preparation method of methyl aceto acetate according to claim 1, it is characterized in that: the mol ratio of ethanol and catalyzer is 0.3～4:1.
7. the preparation method of methyl aceto acetate according to claim 6, it is characterized in that: the mol ratio of ethanol and catalyzer is 1.5～2.5:1.
8. the preparation method of the described methyl aceto acetate of any one right according to claim 1 to 7, it is characterized in that: in the ethanol after gasification, the content of ethanol is more than 99wt%.
9. the preparation method of methyl aceto acetate according to claim 1 is characterized in that: after reaction finished, the product solution that contains methyl aceto acetate was collected in condensation, and rectification under vacuum, obtain purity at the methyl aceto acetate finished product more than 99%.
10. the preparation method of methyl aceto acetate according to claim 9, is characterized in that: reclaim unreacted ethanol and re-use in reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104526614A CN102557939B (en) | 2011-12-30 | 2011-12-30 | Method for preparing ethyl acetoacetate |
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| CN2011104526614A CN102557939B (en) | 2011-12-30 | 2011-12-30 | Method for preparing ethyl acetoacetate |
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| CN102557939A CN102557939A (en) | 2012-07-11 |
| CN102557939B true CN102557939B (en) | 2013-11-13 |
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| CN2011104526614A Active CN102557939B (en) | 2011-12-30 | 2011-12-30 | Method for preparing ethyl acetoacetate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3513189A (en) * | 1968-04-05 | 1970-05-19 | Union Carbide Corp | Preparation of acetoacetic esters |
| CN1062304A (en) * | 1992-01-31 | 1992-07-01 | 清华大学 | The catalyzer that is used for synthesizing ethylester acetate from alcohol alone |
| CN102101829A (en) * | 2009-12-22 | 2011-06-22 | 上海吴泾化工有限公司 | Process for preparing acetoacetic ester |
-
2011
- 2011-12-30 CN CN2011104526614A patent/CN102557939B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3513189A (en) * | 1968-04-05 | 1970-05-19 | Union Carbide Corp | Preparation of acetoacetic esters |
| CN1062304A (en) * | 1992-01-31 | 1992-07-01 | 清华大学 | The catalyzer that is used for synthesizing ethylester acetate from alcohol alone |
| CN102101829A (en) * | 2009-12-22 | 2011-06-22 | 上海吴泾化工有限公司 | Process for preparing acetoacetic ester |
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| CN102557939A (en) | 2012-07-11 |
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Denomination of invention: A Preparation Method of Ethyl Acetoacetate Effective date of registration: 20230410 Granted publication date: 20131113 Pledgee: China Minsheng Bank Co.,Ltd. Suzhou Branch Pledgor: Wujiang Shuguang Chemical Co.,Ltd. Registration number: Y2023980037715 |